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ID 19244
file
creator
Tokue, Ikuo
Nanbu, Shinkoh
abstract
Transition probabilities were evaluated for the X˜ 1A1-A˜ 1B1 and A˜ 1B1-B˜ 1A1 systems of SiH2 and SiD2 to analyze the X˜→A˜→B˜ photoexcitation. The Franck–Condon factors (FCFs) and Einstein's B coefficients were computed by quantum vibrational calculations using the three-dimensional potential energy surfaces (PESs) of the SiH2(X˜ 1A1 ,A˜ 1B1 ,B˜ 1A1) electronic states and the electronic transition moments for the X˜ -A˜, X˜ -B˜, and A˜ -B˜ system. The global PESs were determined by the multireference configuration interaction calculations with the Davidson correction and the interpolant moving least-squares method combined with the Shepard interpolation. The obtained FCFs for the X˜ -A˜ and A˜ -B˜ systems exhibit that the bending mode is strongly enhanced in the excitation since the equilibrium bond angle greatly varies with the three states; the barrier to linearity is evaluated to be 21 900 cm-1 for the X˜ state, 6400 cm-1 for the A˜ state, and 230–240 cm-1 for the B˜ state. The theoretical lifetimes for the pure bending levels of the A˜ and B˜ states were calculated from the fluorescence decay rates for the A˜ -X˜, B˜ -A˜, and B˜ -X˜ emissions.
journal title
Journal of Chemical Physics
volume
Volume 122
issue
Issue 14
start page
144307-1
end page
144307-10
date of issued
2005-04-08
publisher
American Institute of Physics
issn
0021-9606
ncid
publisher doi
language
eng
nii type
Journal Article
HU type
Journal Articles
DCMI type
text
format
application/pdf
text version
publisher
rights
Copyright (c) 2005 American Institute of Physics.
relation url
department
Graduate School of Science